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WO2025110152A1 - Procédé de production de pastilles, procédé de production d'une membrane échangeuse d'ions et pastilles - Google Patents

Procédé de production de pastilles, procédé de production d'une membrane échangeuse d'ions et pastilles Download PDF

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Publication number
WO2025110152A1
WO2025110152A1 PCT/JP2024/040957 JP2024040957W WO2025110152A1 WO 2025110152 A1 WO2025110152 A1 WO 2025110152A1 JP 2024040957 W JP2024040957 W JP 2024040957W WO 2025110152 A1 WO2025110152 A1 WO 2025110152A1
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WIPO (PCT)
Prior art keywords
ion exchange
group
pellets
fluoropolymer
air
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2024/040957
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English (en)
Japanese (ja)
Inventor
慎太朗 早部
康介 角倉
敏亮 澤田
健 小松
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AGC Inc
Original Assignee
Asahi Glass Co Ltd
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Filing date
Publication date
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Publication of WO2025110152A1 publication Critical patent/WO2025110152A1/fr
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • This disclosure relates to a method for producing pellets, a method for producing ion exchange membranes, and pellets.
  • Ion exchange membranes containing fluorine-containing polymers having ion exchange groups are used in various batteries, electrolysis processes, and processes for separating ions and the like.
  • a method for producing an ion exchange membrane containing a fluoropolymer there is known a method using pellets of a fluoropolymer having an ion exchange group or a group that can be converted to an ion exchange group as a raw material.
  • the pellets are produced, for example, by extruding a polymer melt through a die, water-cooling it to form strands, and cutting the strands with a pelletizer (see Patent Document 1).
  • the present inventors referring to the technology described in Patent Document 1, formed an ion exchange membrane using pellets produced from water-cooled strands, and found that the resulting ion exchange membrane sometimes had uneven thickness in the in-plane direction.
  • the unevenness in the in-plane thickness of the ion exchange membrane is required to be small, and therefore there has been a demand for reducing the unevenness in the thickness.
  • an object of one embodiment of the present invention is to provide a method for producing pellets that can be used to produce, via a melt extrusion method, an ion exchange membrane in which in-plane thickness unevenness is suppressed.
  • Another object of one embodiment of the present invention is to provide a method for producing an ion exchange membrane and a pellet.
  • a method for producing pellets comprising extruding a melt containing a fluoropolymer having a group convertible into an ion-exchange group through a die of a melt extruder to obtain a strand containing the fluoropolymer, and then cutting the strand to obtain pellets containing the fluoropolymer, comprising the steps of:
  • the method for producing pellets includes an air-cooling treatment in which air is blown onto the strand extruded from the die to cool it.
  • [2] The method for producing pellets according to [1], wherein the group that can be converted into an ion exchange group is a group that can be converted into a carboxylic acid type functional group or a group that can be converted into a sulfonic acid type functional group.
  • [3] The method for producing pellets according to [1] or [2], wherein in the air-cooling treatment, the water content of the air blown is 22 g/ m3 or less.
  • [4] The method for producing pellets according to any one of [1] to [3], wherein the linear velocity of the air blown is 5.0 to 50.0 m/sec.
  • [5] The method for producing pellets according to any one of [1] to [4], wherein the temperature of the air blown is 40° C.
  • a method for producing pellets that can be used to produce, via a melt extrusion method, an ion exchange membrane in which thickness unevenness in the in-plane direction is suppressed.
  • a method for producing an ion exchange membrane and a pellet can also be provided.
  • ion exchange group refers to a group capable of exchanging at least a portion of the ions contained in this group for other ions, and examples thereof include the following sulfonic acid type functional groups and carboxylic acid type functional groups.
  • sulfonic acid functional group refers to a sulfonic acid group (-SO 3 H) or a sulfonate group.
  • Examples of the form of the sulfonate group include (-SO 3 - )Ma + , (-SO 3 - ) 2Mb 2+ , and (-SO 3 - ) 3Mc 3+ (where Ma + is an alkali metal ion or a quaternary ammonium cation, Mb 2+ is a divalent metal ion, and Mc 3+ is a trivalent metal ion).
  • Ma + is an alkali metal ion or a quaternary ammonium cation
  • Mb 2+ is a divalent metal ion
  • Mc 3+ is a trivalent metal ion
  • carboxylic acid type functional group refers to a carboxylic acid group (-COOH) or a carboxylate salt group.
  • carboxylate salt group examples include ( -COO- )Ma + , (-COO-) 2Mb2 + , and ( -COO- ) 3Mc3 + (where Ma + is an alkali metal ion or a quaternary ammonium cation, Mb2 + is a divalent metal ion, and Mc3 + is a trivalent metal ion).
  • a “precursor membrane” is a membrane that includes a polymer having groups that can be converted to ion-exchange groups.
  • group that can be converted into an ion-exchange group refers to a group that can be converted into an ion-exchange group by a known treatment such as hydrolysis or acidification.
  • group that can be converted into a sulfonic acid functional group refers to a group that can be converted into a sulfonic acid functional group by a known treatment such as hydrolysis treatment or acidification treatment.
  • group that can be converted into a carboxylic acid functional group refers to a group that can be converted into a carboxylic acid functional group by a known treatment such as hydrolysis or acidification.
  • perfluorohydrocarbon group refers to a hydrocarbon group in which all of the hydrogen atoms have been replaced with fluorine atoms.
  • perfluoroaliphatic hydrocarbon group means an aliphatic hydrocarbon group in which all of the hydrogen atoms have been replaced with fluorine atoms.
  • unit in a polymer refers to an atomic group derived from one molecule of a monomer formed by polymerization of the monomer.
  • the unit may be an atomic group formed directly by the polymerization reaction, or may be an atomic group in which part of the atomic group is converted into a different structure by processing the polymer obtained by the polymerization reaction.
  • units derived from individual monomers will sometimes be referred to by the name of the monomer with "unit" added.
  • reinforcing material refers to a material used to improve the strength of the ion exchange membrane.
  • a material derived from a reinforcing cloth is preferable.
  • "Reinforcing fabric” refers to a fabric used as a raw material for a reinforcing material for improving the strength of an ion exchange membrane.
  • a numerical range expressed using “to” means a range including the numerical values described before and after "to” as the lower and upper limits. In addition, when the units of the lower and upper limits are the same, the unit for the lower limit may be omitted.
  • the upper or lower limit described in a certain numerical range may be replaced with the upper or lower limit of another numerical range described in stages.
  • the upper or lower limit described in a certain numerical range may be replaced with a value shown in the examples.
  • the method for producing pellets according to the present disclosure is a method for producing pellets comprising extruding a melt containing a fluoropolymer having a group convertible to an ion-exchange group (hereinafter also referred to as fluoropolymer (I')) through the die of a melt extruder to obtain a strand containing the fluoropolymer, and then cutting the strand to obtain pellets containing the fluoropolymer.
  • the present production method includes an air-cooling treatment in which air is blown against the strand extruded through the die to cool it.
  • the resulting ion exchange membrane has less uneven thickness in the in-plane direction.
  • the fluoropolymer comes into direct contact with water, which may cause hydrolysis of groups that can be converted into ion-exchange groups.
  • Such hydrolysis is more likely to occur on the surface of the strands (parts that come into direct contact with water), and therefore it is believed that hydrolysis occurs non-uniformly in the produced pellets.
  • the present inventors have found that when such hydrolyzed pellets are used to form an ion exchange membrane by melt extrusion, the resulting ion exchange membrane has an uneven thickness.
  • the reason for this uneven thickness is presumably that the hydrolyzed fluoropolymer portion and the non-hydrolyzed fluoropolymer portion in the pellets have different fluidity during melting, causing uneven thickness during melt extrusion.
  • the present production method since the strands are cooled by air-cooling, it is considered that hydrolysis of groups that can be converted to ion-exchange groups is unlikely to occur.
  • a fluoropolymer having a group that can be converted into an ion-exchange group is fed into a melt extruder to obtain a melt of the fluoropolymer.
  • the melt extruder may be a known device, and specific examples thereof include a single screw extruder, a twin screw extruder, and a tandem extruder.
  • the melting temperature of the fluoropolymer (I') is preferably from 150 to 350.degree. C., particularly preferably from 200 to 300.degree.
  • the molten fluoropolymer (I') is extruded from a die at the tip of the melt extruder and cooled to obtain strands containing the fluoropolymer (I'), which are then cut to a predetermined size. In this way, pellets containing the fluoropolymer (I') are obtained.
  • Blowing air means that the linear velocity of the air is 0.3 m/sec or more, and in terms of making the strand thickness more uniform and reducing the unevenness in the film thickness, the linear velocity of the air is preferably 0.6 m/sec or more, more preferably 5.0 m/sec or more, even more preferably 10.0 m/sec or more, and particularly preferably 20.0 m/sec or more.
  • the linear velocity of the air may be 30.0 m/sec or more.
  • the upper limit of the linear velocity of the air is not particularly limited, but may be, for example, 50.0 m/sec or less, and may be 40.0 m/sec or less.
  • the linear velocity of the air is measured by an anemometer, and the detailed measurement method is in accordance with the method described in the Examples. Note that the linear velocity of the air is measured in advance in a state where the strand has not yet been extruded from the die.
  • the air-cooling treatment by blowing air is preferably carried out at least at a point that is 15 to 1 cm away from the die, more preferably 10 to 3 cm, and even more preferably 8 to 5 cm.
  • the range over which air is blown onto the strands is often 10 cm or more in the longitudinal direction of the strands, preferably 1 m or more, more preferably 3 m or more, and even more preferably 5 m or more.
  • the upper limit of the range over which air is blown onto the strands is not particularly limited, but may be, for example, 20 m or less.
  • the air cooling process in which air is blown onto the strand to cool it is preferably performed by blowing air onto the strand in the longitudinal direction thereof, since this is the distance range from the die.
  • the portion where air is blown onto the strands may be one portion, or may be divided into two or more portions.
  • the linear velocity of the air at each portion may be the same in some or all of the portions, or may be different from each other.
  • the strand conveying speed is not particularly limited, but is often 10.0 m/min or less, preferably 5.0 m/min or less, and more preferably 3.0 m/min or less.
  • the strand conveying speed is often 0.5 m/min or more, preferably 1.0 m/min or more, and more preferably 2.0 m/min or more.
  • the above-mentioned conveying speed refers to the distance that one point of the strand moves in one minute.
  • the residence time of the strand in the area where the air-cooling treatment is performed can also be appropriately adjusted.
  • the residence time can be calculated by dividing the length of the area where the air-cooling treatment is performed by the conveying speed.
  • the residence time is often 0.5 minutes or more, preferably 1.0 minutes or more, and more preferably 2.0 minutes or more, and is often 10.0 minutes or less, preferably 7.0 minutes or less, and more preferably 5.0 minutes or less.
  • the air blown in the cooling process may be humidity-conditioned air.
  • the moisture content of the air is preferably 55 g/ m3 or less, more preferably 22 g/m3 or less, even more preferably 18 g/m3 or less , and particularly preferably 14 g/m3 or less , in order to further suppress unevenness in the thickness of the ion exchange membrane in the in-plane direction of the membrane obtained.
  • the lower limit of the moisture content of the air is not particularly limited, but may be 3 g/ m3 or more .
  • the temperature of the air blown in the cooling process may be controlled.
  • the air temperature is preferably 45° C. or less, more preferably 40° C. or less, even more preferably 30° C. or less, and particularly preferably 25° C. or less.
  • the temperature of the die when the melt containing the fluoropolymer (I') is extruded through the die is preferably less than 300°C, more preferably 270°C or less, even more preferably 260°C or less, particularly preferably 240°C or less, and most preferably 200°C or less.
  • the die temperature is preferably 160° C. or higher, more preferably 180° C. or higher, since this facilitates extrusion of the melt of the fluoropolymer (I') from the die.
  • the shape of the pellets obtained by the present production method is not particularly limited, and may be, for example, any shape such as a sphere (including an ellipsoid) or a columnar shape (for example, a cylindrical shape).
  • the size of the pellets obtained by this production method is not particularly limited, but for example, when the pellets are cylindrical, they preferably have a diameter of 2 to 3 mm and a length of 2 to 3 mm.
  • the surface of the pellets (strands) obtained by this production method preferably has a plurality of grooves formed thereon, which makes it possible to prevent the pellets from sticking together.
  • the grooves formed on the surface of the pellet may be formed over the entire surface of the pellet, but it is usually preferred that they are formed only on the side surface of the pellet (surfaces other than the cut surfaces of the strands).
  • the grooves formed on the surface of the pellet are preferably formed mainly along a direction intersecting the cut surface of the pellet (the flow direction of the strand).
  • a roughening treatment may be carried out to roughen the surfaces of the pellets, which makes the surfaces of the pellets more rough, and can further suppress adhesion between the pellets, thereby obtaining an ion exchange membrane with better stability in the electrolysis voltage.
  • a specific example of the surface roughening treatment method is a method in which pellets are stirred using a mixer (for example, a V blender).
  • the pellets obtained by this manufacturing method are preferably used to manufacture ion exchange membranes. Specific examples of uses for ion exchange membranes are described below.
  • the fluoropolymer (I') used in the present production method is a fluoropolymer having a group that can be converted into an ion-exchange group.
  • the group that can be converted into an ion-exchange group is preferably a group that can be converted into a carboxylic acid type functional group or a group that can be converted into a sulfonic acid type functional group.
  • the ion exchange capacity of the fluoropolymer (I') when the groups convertible to ion exchange groups of the fluoropolymer (I) are converted to ion exchange groups is preferably 0.9 meq/g resin or more, more preferably 1.0 meq/g resin or more, even more preferably 1.1 meq/g resin or more, and particularly preferably 1.25 meq/g resin or more, from the viewpoint of reducing the electrolysis voltage of a device incorporating an ion exchange membrane. Also, from the viewpoint of superior strength of the ion exchange membrane, it is preferably 2.00 meq/g resin or less, more preferably 1.90 meq/g resin or less, and even more preferably 1.40 meq/g resin or less.
  • dimethylsulfoxide/potassium hydroxide/water 30/5.5/64.5 (mass ratio) at 95°C for 30 minutes
  • the polymer is immersed in an aqueous sodium hydroxide solution to convert the terminal groups from K-type to Na-type, thereby obtaining the fluoropolymer (I) for measuring the ion exchange capacity.
  • the ion exchange capacity of the thus obtained fluoropolymer (I) can be measured by a method as described later in the Examples section.
  • the fluoropolymer (I') may be used alone or in combination of two or more kinds.
  • the fluoropolymer (I') is preferably a fluoropolymer having a group which can be converted into a carboxylic acid type functional group (hereinafter also referred to as fluoropolymer (C')), or a fluoropolymer having a group which can be converted into a sulfonic acid type functional group (hereinafter also referred to as fluoropolymer (S')), in terms of enabling the effects of the present disclosure to be more effectively exhibited.
  • fluoropolymers will be described in detail below.
  • the fluorine-containing polymer (C') is more preferably a copolymer of a fluorine-containing olefin and a monomer having a fluorine atom and a group that can be converted into a carboxylic acid type functional group (hereinafter also referred to as fluorine-containing monomer (C')), since the effects of the present disclosure can be more effectively exhibited.
  • the copolymerization method may be a known method such as solution polymerization, suspension polymerization, or emulsion polymerization.
  • the fluorine-containing monomer (C') is not particularly limited as long as it is a compound having one or more fluorine atoms in the molecule, an ethylenic double bond, and a group that can be converted into a carboxylic acid functional group, and any conventionally known compound can be used.
  • the fluorine-containing monomer (C') is preferably a monomer represented by the following formula (1) from the viewpoints of the production cost of the monomer, the reactivity with other monomers, and excellent properties of the resulting fluorine-containing polymer.
  • CF 2 CF-(O) p -(CF 2 ) q -(CF 2 CFX) r -(O) s -(CF 2 ) t -(CF 2 CFX') u -A 1
  • X and X' are each independently a fluorine atom or a trifluoromethyl group.
  • a 1 is a group that can be converted into a carboxylic acid type functional group. Specific examples include -CN, -COF, -COOR 1 (R 1 is an alkyl group having 1 to 10 carbon atoms), and -COONR 2 R 3 (R 2 and R 3 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms).
  • p is an integer of 0 or 1.
  • q is an integer of 0 to 12.
  • r is an integer of 0 to 3.
  • s is an integer of 0 or 1.
  • t is an integer of 0 to 12.
  • u is an integer of 0 to 3, provided that 1 ⁇ p+s and 1 ⁇ r+u are satisfied.
  • CF 2 CF-O-CF 2 CF 2 -COOCH 3
  • CF 2 CF-O-CF 2 CF 2 CF 2 -COOCH 3
  • CF 2 CF-O-CF 2 CF 2 -O-CF 2 CF 2 -COOCH 3
  • CF 2 CF-O-CF 2 CF 2 -O-CF 2 CF 2 -COOCH 3
  • CF 2 CF-O-CF 2 CF 2 -O-CF 2 CF 2 CF 2 -COOCH 3
  • CF 2 CF-O-CF 2 CF 2 -O-CF 2 CF 2 CF 2 -COOCH 3
  • CF 2 CF-O-CF 2 CF 2 CF 2 -O-CF 2 CF 2 -COOCH 3
  • CF 2 CF-O-CF 2 CF 2 CF 2 -O-CF 2 CF 2 -COOCH 3
  • CF 2 CF-O-CF 2 CF 2 CF 2 -O-CF 2 CF 2
  • the fluorine-containing olefin may be a fluoroolefin having 2 to 3 carbon atoms and having one or more fluorine atoms in the molecule.
  • Specific examples thereof include tetrafluoroethylene (TFE), chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, and hexafluoropropylene.
  • TFE tetrafluoroethylene
  • chlorotrifluoroethylene chlorotrifluoroethylene
  • vinylidene fluoride vinyl fluoride
  • hexafluoropropylene Among them, TFE is particularly preferred in terms of the production cost of the monomer, reactivity with other monomers, and excellent properties of the resulting fluorine-containing polymer.
  • the fluorine-containing olefins may be used alone or in combination of two or more kinds.
  • the fluorine-containing polymer (C') in addition to the fluorine-containing monomer (C') and the fluorine-containing olefin, other monomers may be used.
  • the other monomers include CF 2 ⁇ CFR f (R f is a perfluoroalkyl group having 2 to 10 carbon atoms), CF 2 ⁇ CF-OR f1 (R f1 is a perfluoroalkyl group having 1 to 10 carbon atoms), and CF 2 ⁇ CFO(CF 2 ) v CF ⁇ CF 2 (v is an integer of 1 to 3).
  • Copolymerization of other monomers can improve the flexibility and mechanical strength of the ion exchange membrane.
  • the content of units based on other monomers is preferably at most 30 mass % based on all units in the fluoropolymer (C') from the viewpoint of maintaining the ion exchange performance.
  • the fluorine-containing polymer (S') is more preferably a copolymer of a fluorine-containing olefin and a monomer having a fluorine atom and a group that can be converted into a sulfonic acid functional group (hereinafter also referred to as fluorine-containing monomer (S')), since the effects of the present disclosure can be more effectively exhibited.
  • the copolymerization method may be a known method such as solution polymerization, suspension polymerization, or emulsion polymerization.
  • the fluorine-containing olefin may be any of those exemplified above, with TFE being preferred from the viewpoints of monomer production cost, reactivity with other monomers, and excellent properties of the resulting fluorine-containing polymer (S').
  • the fluorine-containing olefins may be used alone or in combination of two or more kinds.
  • the content of units based on fluorine-containing olefin based on all units contained in the fluorine-containing polymer (S') is preferably from 65 to 95 mol %.
  • the fluorine-containing monomer (S') may be a compound having one or more fluorine atoms in the molecule, an ethylenic double bond, and a group that can be converted into a sulfonic acid type functional group.
  • a compound represented by formula (2) is preferred from the viewpoints of the production cost of the monomer, the reactivity with other monomers, and excellent properties of the resulting fluorine-containing polymer (S').
  • Formula (2) CF 2 CF-L-(A) n
  • L is an (n+1) valent perfluorohydrocarbon group which may contain an oxygen atom.
  • the oxygen atoms may be located at the terminal ends or between the carbon atoms in the perfluorohydrocarbon group.
  • the number of carbon atoms in the (n+1)-valent perfluorohydrocarbon group is preferably 1 or more, more preferably 2 or more, and is preferably 20 or less, more preferably 10 or less.
  • the divalent perfluoroalkylene group may be either linear or branched.
  • n is an integer of 1 or 2.
  • A is a group that can be converted into a sulfonic acid type functional group.
  • the group that can be converted into a sulfonic acid type functional group is preferably a functional group that can be converted into a sulfonic acid type functional group by hydrolysis.
  • Specific examples of the group that can be converted into a sulfonic acid type functional group include -SO 2 F, -SO 2 Cl, and -SO 2 Br.
  • n is 2, the two As may be the same or different.
  • the compound represented by formula (2) is preferably a compound represented by formula (2-1), a compound represented by formula (2-2), a compound represented by formula (2-3), or a compound represented by formula (2-4).
  • Formula (2-1): CF 2 CF-O-R f1 -A
  • Formula (2-2): CF 2 CF-R f1 -A
  • R f1 is a perfluoroalkylene group which may contain an oxygen atom between carbon atoms.
  • the number of carbon atoms in the perfluoroalkylene group is preferably 1 or more, more preferably 2 or more, and is preferably 20 or less, more preferably 10 or less.
  • R f2 is a single bond or a perfluoroalkylene group which may contain an oxygen atom between carbon atoms.
  • the number of carbon atoms in the perfluoroalkylene group is preferably 1 or more, more preferably 2 or more, and is preferably 20 or less, more preferably 10 or less.
  • r is 0 or 1.
  • R f2 is a single bond or a perfluoroalkylene group which may contain an oxygen atom between the carbon atoms.
  • a in the formula is as described above.
  • R f3 is a single bond or a perfluoroalkylene group which may contain an oxygen atom between carbon atoms.
  • the number of carbon atoms in the perfluoroalkylene group is preferably 1 or more, more preferably 2 or more, and is preferably 20 or less, more preferably 10 or less.
  • r is 0 or 1.
  • m is 0 or 1.
  • w is an integer of 1 to 8
  • x is an integer of 1 to 5.
  • CF 2 CF-O-(CF 2 ) w -SO 2 F
  • CF 2 CF-O-CF 2 CF(CF 3 )-O-(CF 2 ) w -SO 2 F
  • CF 2 CF-[O-CF 2 CF(CF 3 )] x -SO 2 F
  • CF 2 CF-(CF 2 ) w -SO 2 F
  • CF 2 CF-CF 2 -O-(CF 2 ) w -SO 2 F
  • the compound represented by formula (2-3) is preferably a compound represented by formula (2-3-1).
  • R f4 is a linear perfluoroalkylene group having 1 to 6 carbon atoms
  • R f5 is a single bond or a linear perfluoroalkylene group having 1 to 6 carbon atoms which may contain an oxygen atom between the carbon atoms.
  • the definitions of r and A in the formula are as described above.
  • the compound represented by formula (2-4) is preferred.
  • R f1 , R f2 and A are defined as above.
  • the fluorine-containing monomer (S') may be used alone or in combination of two or more kinds.
  • the content of units based on the fluorine-containing monomer (S') relative to all units contained in the fluorine-containing polymer (S') is preferably from 5 to 35 mol %.
  • other monomers may be used in the production of the fluoropolymer (S'). Examples of the other monomers include those exemplified above.
  • the content of units based on other monomers is preferably at most 30 mass % based on all units in the fluoropolymer (S') from the viewpoint of maintaining the ion exchange performance.
  • pellets obtained by the production method of the present disclosure contain a fluoropolymer (fluoropolymer (I')) having a group that can be converted into an ion-exchange group.
  • fluoropolymer (I') fluoropolymer having a group that can be converted into an ion-exchange group.
  • the light transmittance of the pellets is preferably 30 to 60%, more preferably 30 to 50%, and even more preferably 30 to 40%.
  • the pellets having a light transmittance within the above range are presumed to have a roughened surface. This reduces the contact area between the pellets, which is believed to suppress adhesion between the pellets. This suppresses pressure fluctuations during film molding, and provides an ion exchange membrane with excellent uniformity in film thickness.
  • the light transmittance of the pellets means the visible light transmittance (measured at a wavelength of 400 to 700 nm) measured using a visual transmittance meter (manufactured by Asahi Spectroscopy, MODEL 304 or an equivalent device), and the specific measurement method is as follows.
  • the luminous transmittance meter is adjusted so that the visible light transmittance is 100% when no sample holder described below is placed on the sample stage of the luminous transmittance meter.
  • a sample holder with a hole of a predetermined size for fitting a pellet e.g., a rectangular hole 2 to 3 mm long and 2 to 3 mm wide
  • the light intensity is adjusted so that the visible light transmittance is 25% before the pellet is fitted into the hole of the sample holder.
  • a pellet of the same size as the hole of the sample holder is fitted into the hole of the sample holder, and the visible light transmittance is measured.
  • the visible light transmittance of the pellet is measured at multiple points for one pellet, and the arithmetic average value is calculated. For example, if the pellet is cylindrical, the pellet is fitted into the hole of the sample holder so that light is irradiated onto the side of the pellet, and the pellet is rotated 90 degrees in the circumferential direction, and the visible light transmittance is measured at three points for one pellet, and the arithmetic average value is calculated. Then, the visible light transmittance of the pellet is calculated when the visible light transmittance (25%) before the pellet is fitted into the hole in the sample holder is converted to 100% (i.e., the measured visible light transmittance of the pellet is multiplied by 4), and this is regarded as the light transmittance (%) of the pellet.
  • the hydrolysis rate of the pellets is less than 1.00%, preferably less than 0.50%, more preferably less than 0.30%, and even more preferably less than 0.10%.
  • the fluoropolymer (I') contained in the present pellets is the same as the fluoropolymer (I') used in the present production method described above, and the preferred embodiments such as the ion exchange capacity are also the same.
  • the shape, size, surface condition, and uses of the pellets are the same as those of the pellets obtained by the above-mentioned production method.
  • the ion exchange membrane obtained by using the present pellets (hereinafter, also referred to as the present ion exchange membrane) will be described.
  • An example of a suitable method for producing the present ion exchange membrane includes a method in which a precursor membrane containing a fluoropolymer having a group that can be converted into an ion exchange group (fluoropolymer (I')) is formed using the present pellets, and then the group that can be converted into an ion exchange group, which is contained in the precursor membrane, is converted into an ion exchange group to obtain the present ion exchange membrane containing a fluoropolymer having an ion exchange group (fluoropolymer (I)).
  • the method for producing the precursor film includes an extrusion method. Specifically, the pellets are fed to a known melt extruder for film production, and the melt of the pellets is extruded from a nozzle (e.g., a T-die) of the melt extruder to form a film to obtain a precursor film. That is, the method for producing the precursor film includes a melt extrusion method.
  • the melting temperature of the pellets is preferably 150 to 350°C, particularly preferably 200 to 300°C.
  • the precursor membrane may have a reinforcing material embedded therein.
  • the reinforcing material can be embedded in the precursor membrane by known methods. For example, when forming a multi-layered ion exchange membrane, the reinforcing material can be sandwiched between the precursor membranes. The reinforcing material can also be embedded in the precursor membrane by coating both sides of the reinforcing material with a melt of the pellets.
  • reinforcing materials include reinforcing cloth (preferably woven cloth), fibrils, and porous bodies, with reinforcing cloth being preferred among these.
  • the present ion exchange membrane containing the fluoropolymer (I) can be obtained by converting groups that can be converted into ion exchange groups of the fluoropolymer (I') contained in the precursor membrane into ion exchange groups.
  • Specific examples of the method for converting groups in the precursor membrane that can be converted to ion-exchange groups into ion-exchange groups include a method of subjecting the precursor membrane to a hydrolysis treatment or an acid-form treatment. Among these, the method of contacting the precursor film with an alkaline aqueous solution is preferred.
  • the method for contacting the precursor film with the alkaline aqueous solution include a method of immersing the precursor film in the alkaline aqueous solution and a method of spraying the alkaline aqueous solution onto the surface of the precursor film.
  • the temperature of the alkaline aqueous solution is preferably 30° C. or higher and lower than 100° C. from the viewpoint of productivity of the ion exchange membrane, and the contact time between the precursor membrane and the alkaline aqueous solution is preferably 3 to 300 minutes.
  • the alkaline aqueous solution preferably contains an alkali metal hydroxide, a water-soluble organic solvent, and water.
  • the alkali metal hydroxide include sodium hydroxide and potassium hydroxide, and potassium hydroxide is preferred.
  • the alkali metal hydroxide may be used alone or in combination of two or more kinds.
  • the water-soluble organic solvent is an organic solvent that is easily dissolved in water, and specifically, the solubility in 1000 ml of water (20° C.) is preferably 0.1 g or more, and more preferably 0.5 g or more.
  • the water-soluble organic solvent preferably contains at least one selected from the group consisting of aprotic organic solvents, alcohols, and aminoalcohols, and more preferably contains an aprotic organic solvent.
  • the water-soluble organic solvent may be used alone or in combination of two or more.
  • aprotic organic solvent examples include dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone, with dimethyl sulfoxide being preferred.
  • alcohols include methanol, ethanol, isopropanol, butanol, methoxyethoxyethanol, butoxyethanol, butylcarbitol, hexyloxyethanol, octanol, 1-methoxy-2-propanol, and ethylene glycol.
  • amino alcohols include ethanolamine, N-methylethanolamine, N-ethylethanolamine, 1-amino-2-propanol, 1-amino-3-propanol, 2-aminoethoxyethanol, 2-aminothioethoxyethanol, and 2-amino-2-methyl-1-propanol.
  • the content of the alkali metal hydroxide in the alkaline aqueous solution is preferably 1 to 60% by mass.
  • the content of the water-soluble organic solvent in the alkaline aqueous solution is preferably from 1 to 60% by mass.
  • the content of water in the alkaline aqueous solution is preferably 39 to 80% by mass.
  • a treatment for removing the alkaline aqueous solution may be carried out.
  • the alkaline aqueous solution may be removed by washing the ion exchange membrane that has been brought into contact with the alkaline aqueous solution with water.
  • the resulting ion exchange membrane may be subjected to a drying treatment.
  • the drying treatment is preferably a heat treatment, and the heating temperature is preferably 50 to 160° C.
  • the heating time is preferably 0.1 to 24 hours.
  • the ion exchange membrane may be contacted with an aqueous solution containing potassium ions, sodium ions, or hydrogen ions to replace the counter ions (cations) of the ion exchange groups.
  • an aqueous solution containing potassium ions, sodium ions, or hydrogen ions to replace the counter ions (cations) of the ion exchange groups.
  • a hydrophilic layer may be formed on the surface of the precursor membrane or the present ion exchange membrane.
  • the hydrophilic layer may be formed on at least one of the surfaces of the precursor membrane or the present ion exchange membrane.
  • a specific example of the hydrophilic layer is an inorganic particle layer containing inorganic particles.
  • the inorganic particles are preferably excellent in corrosion resistance against acid or alkali and have hydrophilicity.
  • at least one selected from the group consisting of oxides, nitrides and carbides of Group 4 elements or Group 14 elements is preferable, at least one selected from the group consisting of SiO 2 , SiC, ZrO 2 and ZrC is more preferable, and ZrO 2 is particularly preferable.
  • the hydrophilic layer may contain a binder.
  • any known binder used in known hydrophilic layers can be used, such as methyl cellulose and fluorine-containing polymers having sulfonic acid groups.
  • a specific example of a method for forming the hydrophilic layer is a method in which a solution containing inorganic particles and a binder is applied to the precursor membrane or the ion exchange membrane.
  • the ion exchange membrane may be a single layer or a multilayer structure.
  • a multilayer ion exchange membrane can be produced, for example, by using a precursor membrane obtained by laminating multiple layers of a fluorine-containing polymer having groups that can be converted into ion exchange groups by a co-extrusion method.
  • the thickness of the ion exchange membrane is preferably 30 ⁇ m or more, more preferably 40 ⁇ m or more, in order to maintain a certain strength, and is preferably 500 ⁇ m or less, more preferably 300 ⁇ m or less, and even more preferably 180 ⁇ m or less, in order to increase current efficiency and voltage efficiency.
  • the fluoropolymer (I) is a fluoropolymer obtained by converting groups that can be converted into ion-exchange groups of the fluoropolymer (I') contained in the precursor membrane into ion-exchange groups.
  • the fluoropolymer (I) is preferably a fluoropolymer having a carboxylic acid type functional group (hereinafter also referred to as fluoropolymer (C)) or a fluoropolymer having a sulfonic acid type functional group (hereinafter also referred to as fluoropolymer (S)) from the viewpoint of enabling the effects of the present disclosure to be more effectively exhibited.
  • fluoropolymers will be described in detail below.
  • the fluoropolymer (C) is preferably obtained by converting a group of the above-mentioned fluoropolymer (C') which can be converted into a carboxylic acid type functional group, into a carboxylic acid group.
  • the fluoropolymer (C) preferably contains units based on a fluorine-containing olefin and units based on a monomer having a carboxylic acid type functional group and a fluorine atom.
  • the fluorine-containing olefin may be any of those exemplified above.
  • the fluorine-containing olefin-based unit may be contained in one type alone or in two or more types.
  • a unit represented by the following formula (1C) is preferred.
  • X, X', p, q, r, s, t and u are the same as in formula (1) above.
  • the fluoropolymer (C) may contain units based on other monomers other than the units based on a fluorine-containing olefin and the units based on a monomer having a carboxylic acid type functional group and a fluorine atom.
  • Specific examples of the other monomers include those exemplified above.
  • the content of units based on other monomers is preferably 30 mass% or less based on all units in the fluoropolymer (C) from the viewpoint of maintaining the ion exchange performance.
  • the fluoropolymer (S) is preferably obtained by converting a group of the above-mentioned fluoropolymer (S') which can be converted into a sulfonic acid type functional group into a sulfonic acid group.
  • the fluoropolymer (S) preferably contains units based on a fluorine-containing olefin and units based on a monomer having a sulfonic acid type functional group and a fluorine atom.
  • the fluorine-containing olefin may be any of those exemplified above.
  • the fluorine-containing olefin-based unit may be contained in one type alone or in two or more types.
  • MS is a hydrogen atom, an alkali metal or a quaternary ammonium cation.
  • n 2
  • the two MS may be the same or different.
  • the unit represented by formula (2S) is preferably a unit represented by formula (2S-1), a unit represented by formula (2S-2), a unit represented by formula (2S-3), or a unit represented by formula (2S-4).
  • Formula (2S-1) -[CF 2 -CF(-O-R f1 -SO 3 M S )]-
  • Formula (2S-2) -[CF 2 -CF(-R f1 -SO 3 M S )]-
  • R f1 , R f2 , R f3 , r and m are the same as those in formulae (2-1) to (2-4) above.
  • M 2 S is a hydrogen atom, an alkali metal or a quaternary ammonium cation.
  • w is an integer of 1 to 8
  • x is an integer of 1 to 5.
  • M and S in the formula are as described above. -[CF 2 -CF(-O-(CF 2 ) w -SO 3 M S )]- -[CF 2 -CF(-O-CF 2 CF(CF 3 )-O-(CF 2 ) w -SO 3 M S )]- -[CF 2 -CF(-(O-CF 2 CF(CF 3 )) x -SO 3 M S )]-
  • w is an integer of 1 to 8.
  • M and S in the formula are as described above. -[CF 2 -CF(-(CF 2 ) w -SO 3 M S )]- -[CF 2 -CF(-CF 2 -O-(CF 2 ) w -SO 3 M S )]-
  • the unit represented by formula (2S-3) is preferably a unit represented by formula (2S-3-1), in which M and S are defined as above.
  • the unit represented by formula (2S-4) is preferably a unit represented by formula (2S-4-1), in which R f1 , R f2 and M are as defined above.
  • the unit based on a monomer having a sulfonic acid functional group and a fluorine atom may be contained alone or in combination with two or more types.
  • the fluoropolymer (S) may contain units based on other monomers other than the units based on a fluorine-containing olefin and the units based on a monomer having a sulfonic acid type functional group and a fluorine atom.
  • Specific examples of the other monomers include those exemplified above.
  • the content of units based on other monomers is preferably 30 mass% or less based on all units in the fluoropolymer (S) from the viewpoint of maintaining the ion exchange performance.
  • ion exchange membranes include various battery applications such as solid polymer fuel cells, direct methanol fuel cells, redox flow batteries, and air batteries, as well as various electrolysis devices such as solid polymer water electrolysis, alkaline water electrolysis, ozone water electrolysis, salt electrolysis, organic electrolysis, chloride or oxide electrolysis, etc.
  • the membrane can be used as a separator or solid electrode in various types of electrochemical cells for selective cation transport at the binding portion of the cell.
  • the membrane can be used for sensor applications such as various gas sensors, biosensors, light-emitting devices, optical devices, organic sensors, and carbon nanotube solubilization, actuators, and catalyst applications.
  • the ion exchange capacity described in the above [Production of fluoropolymer (S'-1)] to [Production of fluoropolymer (S'-3)] and [Production of fluoropolymer (C'-1)] represents the ion exchange capacity of the fluoropolymer having ion exchange groups obtained by treating the fluoropolymers (S'-1) to (S'-3) and (C'-1) according to the following procedure.
  • Example 1 The fluoropolymer (C'-1) was fed to a melt extruder for producing pellets to obtain a melt of the fluoropolymer (C'-1).
  • the melt was extruded through a die heated to 190°C and cooled by blowing air to obtain a strand (diameter 3.0 mm).
  • the strand was then cut to a length of 3.0 mm to obtain pellets of the fluoropolymer (C'-1).
  • the cooling by blowing air was performed under the condition that the linear velocity of the air was 2 m/sec.
  • the air was blown in a range of 5 m from the point where the strand was 10 cm from the extrusion from the die toward the opposite side from the die.
  • the linear velocity of the air was measured in advance before the extrusion and cooling.
  • the linear velocity of the air was measured with an anemometer (vane type anemometer, Testo 416) at the point where the strand was 10 cm from the extrusion from the die.
  • the strand transport speed was 2.5 m/min.
  • the air to be blown in the above procedure was previously measured to have a temperature of 25° C. and a relative humidity of 61%. In other words, the moisture content of the air was 14 g/m 3. In the tables below, the moisture content of the air is given in units of g/m 3 .
  • the pellets of the fluoropolymer (S'-1) were fed to a melt extruder for film production, and the pellets were melted at 260°C to obtain a molten pellet of the fluoropolymer (S'-1).
  • the resulting molten pellet was extruded through a T-die and formed into a film to obtain a precursor membrane made of the fluoropolymer (S'-1).
  • the membrane was then immersed in an aqueous sodium hydroxide solution to convert the terminal groups from K-type to Na-type, and then dried to obtain an ion exchange membrane with a membrane thickness of 30 ⁇ m.
  • the following evaluations were carried out on the obtained ion exchange membrane.
  • the thickness unevenness in the in-plane direction of the ion exchange membrane obtained in the latter step was measured.
  • the thickness unevenness in the in-plane direction of the ion exchange membrane was measured at 100 arbitrary points in a 20 cm square area of the obtained ion exchange membrane using a contact type thickness meter, and the thickness unevenness in the in-plane direction of the ion exchange membrane was evaluated according to the following criteria. Note that, in practical terms, an A rating or a B rating is preferable, and an A rating is more preferable.
  • A The thickness measured at any 100 points is within the range of 30 ⁇ m ⁇ 2 ⁇ m at all points.
  • B The thickness measured at any 100 points is not within the range of 30 ⁇ m ⁇ 2 ⁇ m at some points, but is within the range of 30 ⁇ m ⁇ 3 ⁇ m at all points.
  • C The thickness measured at any 100 points is not within the range of 30 ⁇ m ⁇ 3 ⁇ m at any point.
  • Examples 2 to 9 Pellets and ion exchange membranes were prepared and the above measurements and evaluations were carried out in the same manner as in Example 1, except that one or more of the type of fluoropolymer used for producing pellets, the linear velocity of the air blown during pellet production, and the water content of the air were changed as shown in Table 1 below. The results are shown in Table 1. However, in the measurement of the hydrolysis rate, when the group that can be converted into an ion exchange group was --SO.sub.2F , the hydrolysis rate was determined by the following method. First, the number of ion exchange groups was determined from the ion exchange capacity determined by the above-mentioned method. Next, a predetermined amount of pellets was subjected to extraction treatment at 50° C.
  • Example 10 Pellets and an ion exchange membrane were prepared in the same manner as in Example 1, except that the molten material was extruded through a die and cooled with water at 40° C. or less, and the above measurements and evaluations were carried out. The results are shown in Table 1.
  • Example 11 Pellets and an ion exchange membrane were prepared in the same manner as in Example 1, except that the molten material was extruded through a die and cooled in air without blowing air thereon, and the above measurements and evaluations were carried out. The results are shown in Table 1.

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Abstract

L'invention concerne un procédé de production de pastilles qui permettent de produire une membrane échangeuse d'ions, dans laquelle une irrégularité d'épaisseur de film dans la direction dans le plan est supprimée, au moyen d'un procédé d'extrusion à l'état fondu.　Dans ce procédé de production de pastilles, une masse fondue qui contient un polymère contenant du fluor ayant un groupe qui peut être converti en un groupe d'échange d'ions est extrudée à partir d'une filière d'une extrudeuse de matière fondue de façon à obtenir un brin qui contient le polymère contenant du fluor, et le brin est ensuite coupé de façon à obtenir des pastilles qui contiennent le polymère contenant du fluor. Le procédé de production de pastilles comprend un traitement de refroidissement par air pour souffler de l'air sur le brin extrudé à partir de la filière de façon à refroidir le brin.
PCT/JP2024/040957 2023-11-22 2024-11-19 Procédé de production de pastilles, procédé de production d'une membrane échangeuse d'ions et pastilles Pending WO2025110152A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017021181A (ja) * 2015-07-10 2017-01-26 コニカミノルタ株式会社 光学フィルム、偏光板および画像表示装置
JP2018517035A (ja) * 2015-05-27 2018-06-28 ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． 低結晶化度フルオロポリマー粒子のための粘着防止処理
JP2021181539A (ja) * 2020-05-19 2021-11-25 Ａｇｃエンジニアリング株式会社 複合粒子、成形体、中空糸膜の製造方法、イオン交換膜の製造方法
WO2022249993A1 (fr) * 2021-05-25 2022-12-01 Ａｇｃ株式会社 Composition de résine, son procédé de production et corps moulé
WO2023085421A1 (fr) * 2021-11-15 2023-05-19 Ａｇｃ株式会社 Composition de résine, objet moulé, composite et son utilisation
JP2023083531A (ja) * 2018-09-14 2023-06-15 Ａｇｃ株式会社 ペレットの製造方法、ペレット及びイオン交換膜

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018517035A (ja) * 2015-05-27 2018-06-28 ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． 低結晶化度フルオロポリマー粒子のための粘着防止処理
JP2017021181A (ja) * 2015-07-10 2017-01-26 コニカミノルタ株式会社 光学フィルム、偏光板および画像表示装置
JP2023083531A (ja) * 2018-09-14 2023-06-15 Ａｇｃ株式会社 ペレットの製造方法、ペレット及びイオン交換膜
JP2021181539A (ja) * 2020-05-19 2021-11-25 Ａｇｃエンジニアリング株式会社 複合粒子、成形体、中空糸膜の製造方法、イオン交換膜の製造方法
WO2022249993A1 (fr) * 2021-05-25 2022-12-01 Ａｇｃ株式会社 Composition de résine, son procédé de production et corps moulé
WO2023085421A1 (fr) * 2021-11-15 2023-05-19 Ａｇｃ株式会社 Composition de résine, objet moulé, composite et son utilisation

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